Preparation of polyalkylbenzyl phenols



Parental-ebb, m 4

can undo, Woodbnry, and Howard 1). Hartough, Pitman, N. 1., aseignors to Socony- ;Vaennm Oil Company, Incorporated, a corporation of New York No Drawing. Application September 14, 1944, Serial No. 554,163 1 a claims. (01. 252-42) The present invention relates to the preparation of monoand poly- (polyalkylaralkyl) monohydric and polyhydric mononuclear and polynuclear phenols and more particularly to the preparation 01' polymethyl benzyl monohydric and polyhydric mononuclear and polynuclear phenols. 5

Those skilled in the artare aware that some alkylated phenolic compounds have an excellent stabilizing action upon hydrocarbon oils. However, it has been shown in United States Patent No. 2,202,877 that the stabilizing action of aikylated phenols depends upon the type of alkyl groups introduced in the valkylation process and upon the position of the preferred alkyl groups on the phenolic nucleus. For example, the disclosure of'the aforementioned United States Patent teaches that 2,4,6-trimethyl phenol is not nearly so effective a stabilizer io'r hydrocarbon oils as is 2,6-di-tertiar'y-butyl para cresol (2,6-ditertiary butyl,4-methyl phenol) and that 2,4-ditertiary butyl meta or ortho cresol are much lessefiective than the latter.

It has now been discovered that polyalkylbenzyl monohydric and polyhydric mononuclear and polynuclear phenols have a stabilizing eflect upon hydrocarbon oils.

It is an object of the present invention to provide a process for preparing monoand poly- (polyalkylaralkyl) monohydric and polyhydric, mononuciear and polynuclear phenols. It is an other object of the present invention to prepare phenols oi the aforesaid class from phenolic compounds and halogenated aromatic compounds obtained from petroleum oil. It is a further object oi the present invention to provide a method for producing monoand poly- (polyalkylbenzyl) monohydric and polyhydric monoand polynuclear phenols. The present invention likewise contemplates the production of stabilized hydrocarbon oils containing small but efiective amounts of at least one of the aforesaid monoand poly- (polyalkylaralkyl) monoand polyhydricmonoand polynuclear phenols. Other objects and advantages will become apparent from the following description.

As has been disclosed in the copending application Serial No. 515,145 filed December 21, 19%,

i. e. acyclic and alicyclic hydrocarbons.

mercialiy. This fraction consists essentially of polyalkylated benzenes mixed with non-aromatic, I For the purpose 0! illustrating, but not limiting the pres 'ent invention, the preparation 01 monoand poly- ,(polyalkylaralkyl), monoand polyhydric, monoand polynuclear phenols will be described in conjunction with the use of this fraction as in the name of Howard D. Hartough certain fractions of petroleum oil and particularly fractions of petroleum oil which have been subjected to cracking conditions contain alkylated monoand polynuclear aromatic hydrocarbons. it fraction of cracked oil having a boiling range about 155 0. to about 200 C. is available com one of the components of the reaction.

As has been described in the copending application, Serial No. 515,145 filed December 21, 1943, in the name of Howard D. Hartough the polyalkylbenzyl chlorides employed in the process of the present invention may be produced from aromatic petroleum stocks containing a relatively high percentage of aromatic hydrocarbon constituents such as stocks derived from Houdry.

crackingoperations and commercial operations.

The aromatic hydrocarbons that occur in such stocks are believed to be primarily polymethyl benaenes ranging from trimethyl benzene to tetramethyl benzene. It is possible that small amounts of other aromatic hydrocarbons, such as ethyimethyl benzene may be present also. There are three trimethyl benzenes, mesitylene or 1,3,5-trimethyl benzene; pseudocumene or 1,2,4-trimethyl benzene; and hemimellitene or 1,2,3-trimethyl benzene. Likewise, there are three tetraniethyl benzenes, durene or l,2,i,5-tetramethyl benzene; isodurene or l,2,3,5-tetramethyl benzene; and prehnitene or 1,2,3Ai-tetramethyl benzene. The trimethyl benzenes con stitute the predominant portion of the polyalkylated benzenes present in stocks such as those to which reference is made hereinbefore. For ex. ample, if a stock of the type described herein"- before and having a boiling range of about 155 C. to about 200 C. and containing per cent aromatic hydrocarbons, is subjected to distillation, the fraction boiling between 150 C. and 182 C. will contain per cent aromatic hydrocarbons and will constitute per cent oi the original Sovasol #75 stock. This temperature range (L-182 C.) includes the boiling points of the trimethyl benzenes, but does not include the boiling points of the tetramethyl benzenes. Stated differently, the 75 per cent distillate contains about 82 per cent of the aromatic hydrocarbons originally present in the stock having a boiling range of about C. to about 200 C. that bcilwithin'the boiling range of trimethyl benzenes.

The polyalhylarallryi chlorides employed inthe condensation reaction of the present invention may be produced in the following manner illustrated by the preparation of methylbenzyl chlorides from a hereinbefore described stock having a boiling range of about 155 C. to about 200 C. The aforedescribed aromatic petroleum stock is mixed with any alkyl aldehyde such as formaldehyde, acetaldehyde, etc., in the proportion of 1000 grams of the aforesaid aromatic petroleum stock to about 165 to about 330 grams of 37 per cent formalin solution. About 825 cc. to about 1600 cc. of concentrated hydrochloric acid are added to the aromatic petroleum stockvformalin mixture and a stream of hydrogen chloride passed through the mixture. The temperature is maintained between about 60 C. and about 70 C. for about 6 hours. At the end of the period agitation is stopped and an aqueous layer separated. The hydrocarbon layer is thoroughly washed with water to remove excess hydrochloric acid and aldehyde. The hydrocarbon layer is dried, preferably over calcium chloride and fractionated, the portion distilling over at 110 C. to 130 C. at 10 millimeters pressure being a mixture of chloromethylated aromatic hydrocarbons or polyalkylbenzyl chlorides. The still residue contains dichioromethylated compounds. These polyalkylbenzyl chlorides are then reacted with monoor polyhydric, monoor polynuclear phenols or mixtures thereof to produce the monoand poly- (polyalkylaralkyl) monohydric and polyhydric, monoand polynuclear phenols of this invention. So far as we are aware no one has free reaction product and washing the filtrate of this residue boiling at 200 C. to 225? C. at

prepared alkylated phenolic compounds by the condensation of phenol, polyhydrlc phenols or polynuciear phenols such as naphthols with polyallrylbenzyl chlorides obtained from petroleum oil.

Furthermore, we have found that the conditions under which the condensation of the phenol and the polyalkylaralkyl halide takes place has a marked effect upon the properties of the reaction product. The solubility in hydrocarbon oils of lubricating range appears to be dependent upon the method of preparation and the stabilizing efiect of the products apparently differs in accordance with the method of preparation. Thus, when the reaction is carried out in the presence of an inert solvent the effectiveness of the product as a stabilizer for hydrocarbon oils is impaired or substantially destroyed.

The production of monoand poiy-(polyalkylaralkyl) monoand poiynuclear and monoand polyhydric phenols will be illustrated first and then the effect of the conditions under which the condensation takes place will be described.

Examns I Mono-(polyalkylbenzyl) phenol One hundred and ninety three' '(193) grams (1.1 moles) of polyalkylbenzyl chlorides from aromatic petroleum stock having a. boiling range of about 155 C. to about 200 C. and 180 grams (1.9 moles) of phenol were added to 400 milliliters of xylene. After standing at room temperature (15 C.- C.) for a few minutes hydrogen chloride was evolved. The temperature was raised slowly to the temperature at which xylene refluxed (135 C. to 140 C.) and held at this temperature for six hours. Excess phenol and traces of chlorine preferably are then removed. This can readily be accomplished by cooling the reaction mixture, adding a small amount of zinc dust and refluxing the mixture for a short time to remove the last traces of chlorine from the product. The excess phenol preferably can be removed by filtering the substantially chlorine 10 millimeters of mercury was recovered in the amount of 180 grams and found to be a mixture of ortho and para mono-(polyalkylbenzyl) phenol. An undistillable residue of 50 grams of polybenzylated phenol was also obtained. The 180 grams of ortho and para mono-(polyalkylbenzyl) phenol represents, per cent of theo retical based on the amount of phenol used.

EXAMPLE II Di-(polyalkylbenzyl) resorcinol Thirty grams (0.27 mole) of resorcinol were dissolved in milliliters of xylene and 85 grams (0.50 mole) of polyalkylbenzyl chlorides from aromatic petroleum stockhaving a boiling range of about 155 C. to about 200 C. were added. The mixture was heated to the reflux temperature of the solvent C. to C.) and held at that temperature for about three hours. When desirable, traces of chlorine may be removed, as is preferred, by adding one gram of zinc dust and refluxing the material for about 0.5 hour longer. The mixture was then filtered, water-washed and solvent removed. A dark red, brittle, resinous material was obtained. This resinous material was decidedly more soluble in hydrocarbon oils than the reaction product obtained. in the next example.

Those skilled in the art will understand from the foregoing that to obtain mono-substituted phenols the polyalkylaralkyl halides are reacted with the phenols in the proportion of about 1.1 moles of the former to about 1.9 moles of the phenol. In other words, the halide is reacted with an excess of phenol to produce the monosubstituted phenol; the halides and the phenol are reacted in about stolchiometric proportion to produce the di-substituted phenol.

Illustrative of the efiect of carrying out the reaction in the absence of a solvent is the following procedure in which the polyalkylaralkyl halides and the phenol were reacted in the proportion to produce a di-substituted phenol. That is to say, in the proportion of 0.51 mole of phenol to 1.02 moles of polyalkylaralkyl halide.

EXAMPLE III Twenty-four grams (0.255 mole) of phenol were added to 87 grams (0.51 mole) of polyalkylbenzyl chlorides from aromatic petroleum stock having a boiling range of about C. to about 200 C. The mixture was slowly heated to about 125 C. and held at that temperature until the evolution of hydrogen chloride had ceased. This normally requires about 3 to about 5 hours. In other words, the mixture is slowly heated at least to a temperature at which the reaction takes place as evidenced by the evolution of hydrogen halide and held at that temperature until the reaction is substantially complete as indicated by the cessation of the evolution of hydrogen halide. This temperature varies for different phenols and different polyalkylaralkyl halides but is normally between about 50 C. and about 125 C. After the evolution of hydrogen halide has ceased it is preferred to remove traces of halide by adding a small amount of zinc dust. Accordingly, after the reaction mixture had cooled one gram of zinc dust was added and the mixture refluxed for Table I! 2, 6-di-tertiary butyl, 4-methyl phenol 95 "Dibenzyl cathechol 20 "Dibenzyl resorcinol 36 "Dibenzyl phenol reaction product 73 Dibenzyl p-cresol reaction product 114 Dibenzyl resorcinol reaction product" 171 The foregoing tabulation clearly shows that the reaction products produced when the condensation reaction is carried out in the absence of a diluent are more eflective stabilizers than the products obtained when an inert solvent is used. This tabulation also shows that under the condi- Table V H180 refined oil Solvent 1' oil Material 332, H M H M cuts 8 ours g tested sludge tested sludge Monobenzyl phenoL. 0. 2 312 1. 3 21 605 2; 9 462 Dibenzyl phenol--- 0. 2 328 3. 40 328 0. 08 5. Tribenzyl phenol 0. 2 331 2. 6 32 463 1. 1 l2 Dibenzyl o-cresol 0. 2 330 3. 0 so 330 1. 4 16 Dibenzyl m-cresol.. 0. 2 306 1. 5 12 300 2 1 2i Dibenzyl hydroquinone 0. 2 236 1.6 17 2256 4. 5 422 Dibenzyl pyrogalloi. 0. 2 474 1. l 26 546 7. 0 194 Dibenzyl naphthol.-. 0. 2 375 2. 1 22 501 l. 7 3

tions of this test the "dibenzyl resorcinol reaction product is about '10 per cent more efiective than 2,6-dl-tertiary butyl, 4-methyl phenol in protecting acid refined oil.

When these additives are evaluated in the same manner for solvent refined oil the order of efiectiveness is as follows:

Table III 2, 6-di-tertiary butyl, 4-methyl phenol -1. 3 Dibenzyl phenol reaction product 3 (2.8) Dibenzyl resorcinol reaction product 9 Dibenzyl resorcinol 11 Dibenzy catechol" 16 Dibenzyl p-cresol reaction product 28 The foregoing tabulation clearly shows that the dibenzyl phenol reaction product has about the same protective value for solvent refined oil as 2, 6-di-tertiary butyl, 4-methyl phenol and that the polyhydric phenols are more effective stabilizers in solvent refined oil than the 2, 6-ditertiary butyl, 4-methyl phenol when evaluated by this method.

The following tabulation indicates that dibenzyl p-cresol reaction product and dibenzyl resorcinol reaction product are the most effective stabilizers for acid refined oil while dibenzyl p-cresol'reaction product and "dibenzyl catechol are the most effective for solvent refined oil being about nine and five times as effective, respectively, as 2,6-di-tertiary butyl, 4-methyl phenol.

- Table IV H1804 Refined Solvent Refined N. N. Sludge N. N. Sludge 1 2,6-gl-tertiarybutyl,i-methyl 16 95 3 3 en 2 'fl lbenzylcatechol 14 20 96 16 3 Dibenzylrasorclnol" 35 36 11 ll 4 Dibnntrl phenol reaction 109 73 7 a r uc 5 l ibenzyl resorcinolreaction 6 sure. p. m. "1' a... "sproduct" 171 114 as Although the present invention has been described in terms of the condensation of certain monoand polynuclear, mono-- and polyhydric phenols with polyalkylbenzyl chlorides derived from a particular fraction of aromatic petroleum stock, other polyalkylaralkyl chlorides may be used as well as other phenols as those skilled in the art will understand. Therefore the condensations described hereinbefore are to be considered illustrative of analogous condensations which may, be made employing other aralkyl chlorides and other phenols.

We claim:

1. Hydrocarbon 011 containing a small proportion, 'sufiflcient to stabilize said oil against deterioration from oxidation of the reaction product obtained by reacting polyaikylaralkyl halides with a phenol in the mole] ratio of about 1 to about 2 to about 2 to about 1 at elevated temperatures in the absence of a solvent.

2. Hydrocarbon 011 containing a small proportion, sufficient to stabilize said oil against deterioration from oxidation, of a reaction product obtained by reacting about 0.27 mole of resorcinol with about 0.50 mole of polyalkylbenzyl chlorides at 125 degrees centigrade in the absence of a solvent until evolution of hydrogen chloride is no longer detectable.

3. Hydrocarbon oil containing a small propor not obtained by reacting about 0.27 mole of cateohm with about 0.50 mole of polyalkylbenzyl chlorides at degrees centigrade in the absence of a solvent until the evolution of hydrogen chloride is no longer detectable.

4. Acid refined petroleum oil containing a small proportion, sufficient to stabilize said oil against deterioration from oxidation, of a reaction product obtained by reacting about 0.27 mole of resorclnol with about 0.50 mole of polyalkylbenzyl halides at 125 degrees centigrade in the absence of a solvent until the evolution of hydrogen halide is no longer detectabla- 5. Refined petroleum oil containing a small proportion, sufiicient to stabilize said oil against deterioration from oxidation, of dibenzyl p-cresol reaction-product obtained byireacting'l p-cresol.

and polyallwlbenzyl halides in the molal' ratio of about 1 to about 2 at elevated temperatures in the absence of a diluent.

6. Acid refined petroleum oil containingabout 0.2 p'er cent by weight of dibenzyl resorcinol reaction product obtained by reacting resorcinol and polyalkylbenzyl halides in the molal ratio of about 1- to' about 2 ata temperature of about 125 C. in the absence of a diluent.

REFERENCES CITED m The following references areof record in the 7. Refined petroleum oil containing about 0.2

per cent by weight of dibenzyl p-cresol reaction product obtained by reacting p-cresol and polyalkylbenzyl halides in the molal ratio of about 1 to about 2 at elevated temperatures in the absence of a diluent.

8. Refined petroleum oil containing a small proportion, suflicient to stabilize said oil against deterioration from oxidation, of a reaction prodw file of this patent: UNITED STATESPATENTS Number Name Date 1,593,080 Jordan July 20, 1926 2,116,220 Shoemaker May 3, 1938 2,247,402 Perkins July 1, 1941 2,298g660 Stevens Oct. 13, 1942 2,330,722 Lieber Sept. 28, 1943 2,351,347 Luten June 13, 1944 

